U.S. patent application number 14/495400 was filed with the patent office on 2015-03-05 for material for organic electronic device, and organic electronic device using the same.
The applicant listed for this patent is LG CHEM, LTD.. Invention is credited to Heungwoo CHOI, Sang Young JEON, Hyoung Seok KIM, Hyoungcheul KIM, Kongkyeom KIM, Minjun KIM, Seong So KIM, Kidong KOO, Hyok Joon KWON.
Application Number | 20150060833 14/495400 |
Document ID | / |
Family ID | 52581901 |
Filed Date | 2015-03-05 |
United States Patent
Application |
20150060833 |
Kind Code |
A1 |
KWON; Hyok Joon ; et
al. |
March 5, 2015 |
MATERIAL FOR ORGANIC ELECTRONIC DEVICE, AND ORGANIC ELECTRONIC
DEVICE USING THE SAME
Abstract
The present specification provides a novel compound that is
capable of largely improving an expected life span, efficiency,
electrochemical stability, and thermal stability of an organic
electronic device, and an organic electronic device that includes
an organic material layer including the compound.
Inventors: |
KWON; Hyok Joon; (Daejeon,
KR) ; KOO; Kidong; (Daejeon, KR) ; KIM;
Kongkyeom; (Daejeon, KR) ; KIM; Minjun;
(Daejeon, KR) ; KIM; Seong So; (Daejeon, KR)
; KIM; Hyoung Seok; (Daejeon, KR) ; KIM;
Hyoungcheul; (Daejeon, KR) ; JEON; Sang Young;
(Daejeon, KR) ; CHOI; Heungwoo; (Daejeon,
KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG CHEM, LTD. |
Seoul |
|
KR |
|
|
Family ID: |
52581901 |
Appl. No.: |
14/495400 |
Filed: |
September 24, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13060248 |
May 18, 2011 |
|
|
|
PCT/KR2009/004689 |
Aug 21, 2009 |
|
|
|
14495400 |
|
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Current U.S.
Class: |
257/40 ; 544/284;
548/420 |
Current CPC
Class: |
H01L 51/0052 20130101;
H01L 51/0067 20130101; H01L 51/0072 20130101; H01L 51/5016
20130101 |
Class at
Publication: |
257/40 ; 548/420;
544/284 |
International
Class: |
H01L 51/00 20060101
H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 22, 2008 |
KR |
10-2008-0082477 |
Claims
1. A compound that is represented by the following Formula 1:
##STR00127## wherein in Formula 1, R3 and R4 are bonded to each
other to form an aromatic ring, at least one of a group at which an
aromatic ring is not formed among R1 to R4, a substituent group
that is substituted at an aromatic ring that is formed by bonding
R3 and R4 to each other, and R5 to R8 is -(L1)p-(Y1)q, herein, p is
an integer of 0 to 10, q is an integer of 1 to 10, the remains are
each independently -(L2)r-(Y2)s, herein, r is an integer of 0 to
10, and s is an integer of 1 to 10, X is -(A)m-(B)n, herein, m is
an integer of 0 to 10, and n is independently an integer of 1 to
10, A is an arylene group having 6 to 12 carbon atoms; an
alkenylene group; a fluorenylene group; or a heteroarylene group
including one or more of N, O, and S atoms, in the case where m is
0, B is hydrogen; deuterium; an alkyl group; an alkenyl group; a
silyl group; a boron group; an aryl group having 6 to 12 carbon
atoms; a fluorenyl group; or a hetero ring group including one or
more of N, O, and S atoms, in the case where m is not 0, B is
hydrogen; deuterium; a halogen group; a nitrile group; a nitro
group; a hydroxy group; an alkyl group; a cycloalkyl group; an
alkoxy group; an alkylthioxy group; an alkylsulfoxy group; an
alkenyl group; a silyl group; a boron group; an aryl group having 6
to 12 carbon atoms; a fluorenyl group; or a hetero ring group
including one or more of N, O, and S atoms and unsubstituted or
substituted by an aryl group having 6 to 12 carbon atoms, L1 and L2
are the same as or different from each other, and are each
independently an arylene group having 6 to 12 carbon atoms; an
alkenylene group; a fluorenylene group; a carbazolylene group; or a
heteroarylene group including one or more of N, O, and S atoms, Y1
is a carbazole group unsubstituted or substituted by at least one
of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl
group, an anthracenyl group, a phenanthryl group, a perylenyl
group, a chrysenyl group, a hetero ring group, and an alkylamine
group; or a benzocarbazole group unsubstituted or substituted by at
least one of a phenyl group, a biphenyl group, a terphenyl group, a
naphthyl group, an anthracenyl group, a phenanthryl group, a
perylenyl group, a chrysenyl group, a hetero ring group, and an
alkylamine group, Y2 is hydrogen; deuterium; a halogen group; a
nitrile group; a nitro group; a hydroxy group; an alkyl group; a
cycloalkyl group; an alkoxy group; an alkylthioxy group; an
alkylsulfoxy group; an alkenyl group; a silyl group; a boron group;
an alkylamine group; a fluorenyl group; a carbazole group; or a
hetero ring group including one or more of N, O, and S atoms, and
in the case where two or more of A, B, L1, L2, Y1, or Y2 are
provided, they are the same as or different from each other.
2. The compound of claim 1, wherein Y1 is any one of the following
Formulas 2 to 5: ##STR00128## wherein in Formulas 2 to 5, A1 to A8
are each independently a phenyl group, a biphenyl group, a
terphenyl group, a naphthyl group, an anthracenyl group, a
phenanthryl group, a perylenyl group, a chrysenyl group, a hetero
ring group, or an alkylamine group, a1 is an integer of 0 to 8, a2
is an integer of 0 to 4, a3 is an integer of 0 to 6, a4 is an
integer of 0 to 7, a6 is an integer of 0 to 4, a8 is an integer of
0 to 6, 0.ltoreq.a6+a8.ltoreq.9, and in the case where two or more
of A1, A2, A3, A4, A6, and A8 are provided, they are the same as or
different from each other.
3. The compound of claim 2, wherein A5 and A7 are each
independently a phenyl group, a biphenyl group, a terphenyl group,
a naphthyl group, an anthracenyl group, a phenanthryl group, a
perylenyl group, or a chrysenyl group.
4. The compound of claim 1, wherein the compound represented by
Formula 1 is represented by the following Formula 6: ##STR00129##
wherein in Formula 6, at least one of R1 to R10 is -(L1)p-(Y1)q,
the remains are each independently -(L2)r-(Y2)s, and herein, X, L1,
L2, Y1, Y2, p, q, r, and s are the same as those defined by Formula
1.
5. The compound of claim 1, wherein L1 and L2 are a direct
bond.
6. The compound of claim 1, wherein Y2 is hydrogen.
7. The compound of claim 1, wherein the compound represented by
Formula 1 is represented by any one of the following Formulas 7 to
14: ##STR00130## ##STR00131## ##STR00132## wherein in Formulas 7 to
14, R1, R2, and E1 to E9 are each independently -(L1)p-(Y1)q or
-(L2)r-(Y2)s, wherein A1 to A8 are each independently a phenyl
group, a biphenyl group, a terphenyl group, a naphthyl group, an
anthracenyl group, a phenanthryl group, a perylenyl group, a
chrysenyl group, a hetero ring group, or an alkylamine group, a1 is
an integer of 0 to 8, a2 is an integer of 0 to 4, a3 is an integer
of 0 to 6, a4 is an integer of 0 to 7, a6 is an integer of 0 to 4,
a8 is an integer of 0 to 6, 0.ltoreq.a6+a8.ltoreq.9, e9 is an
integer of 0 to 5, in the case where two or more of A1, A2, A3, A4,
A6, A8, and E9 are provided, they are the same as or different from
each other, and herein, X, L1, L2, Y1, Y2, p, q, r, and s are the
same as those defined by Formula 1.
8. The compound of claim 7, wherein A5 and A7 are each
independently a phenyl group, a biphenyl group, a terphenyl group,
a naphthyl group, an anthracenyl group, a phenanthryl group, a
perylenyl group, or a chrysenyl group.
9. The compound of claim 7, wherein at least one of R1, R2, and E1
to E9 is hydrogen.
10. The compound of claim 1, wherein A is an arylene group having 6
to 12 carbon atoms; or a heteroarylene group including one or more
of N, O, and S atoms, in the case where m is 0, B is an aryl group
having 6 to 12 carbon atoms; a fluorenyl group; or a hetero ring
group including one or more of N, O, and S atoms, and in the case
where m is not 0, B is hydrogen; a nitrile group; a silyl group; an
aryl group having 6 to 12 carbon atoms; a fluorenyl group; or a
hetero ring group including one or more of N, O, and S atoms and
unsubstituted or substituted by an aryl group having 6 to 12 carbon
atoms.
11. The compound of claim 1, wherein m is an integer of 0 to 2, and
n is 1.
12. The compound of claim 1, wherein the compound represented by
Formula 1 is represented by any one of the following Formulas 15 to
30: ##STR00133## ##STR00134## ##STR00135## ##STR00136##
##STR00137## wherein in Formulas 15 to 30, R1 to R10 are each
independently -(L1)p-(Y1)q or -(L2)r-(Y2)s, A1 to A8 are each
independently a phenyl group, a biphenyl group, a terphenyl group,
a naphthyl group, an anthracenyl group, a phenanthryl group, a
perylenyl group, a chrysenyl group, a hetero ring group, or an
alkylamine group, a1 is an integer of 0 to 8, a2 is an integer of 0
to 4, a3 is an integer of 0 to 6, a4 is an integer of 0 to 7, a6 is
an integer of 0 to 4, a8 is an integer of 0 to 6,
0.ltoreq.a6+a8.ltoreq.9, in the case where two or more of A1, A2,
A3, A4, A6, and A8 are provided, they are the same as or different
from each other, and herein, X, L1, L2, Y1, Y2, p, q, r, and s are
the same as those defined by Formula 1.
13. The compound of claim 1, wherein the compound represented by
Formula 1 is represented by any one of the following Formulas 31 to
38: ##STR00138## ##STR00139## ##STR00140## ##STR00141## wherein in
Formulas 31 to 42, R1 to R10 are each independently -(L1)p-(Y1)q or
-(L2)r-(Y2)s, A2, A3 and A6 to A8 are each independently a phenyl
group, a biphenyl group, a terphenyl group, a naphthyl group, an
anthracenyl group, a phenanthryl group, a perylenyl group, a
chrysenyl group, a hetero ring group, or an alkylamine group, a2 is
an integer of 0 to 4, a3 is an integer of 0 to 6, a6 is an integer
of 0 to 4, a8 is an integer of 0 to 6, 0.ltoreq.a6+a8.ltoreq.9, in
the case where two or more of A2, A3, A6 and A8 are provided, they
are the same as or different from each other, and herein, X, L1,
L2, Y1, Y2, p, q, r, and s are the same as those defined by Formula
1.
14. The compound of claim 1, wherein the heteroarylene group of A
is a heteroarylene group including one or more N atoms.
15. The compound of claim 1, wherein the heteroarylene group of A
is a divalent quinazoline group, a divalent carbazole group, or a
divalent pyridine group.
16. The compound of claim 1, wherein X of Formula 1 is selected
from substituent groups described in the following [Table A-1]:
TABLE-US-00004 TABLE A-1 ##STR00142## ##STR00143## ##STR00144##
##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149##
##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154##
##STR00155## ##STR00156## ##STR00157## ##STR00158##
##STR00159##
17. The compound of claim 1, wherein -(L1).sub.p--(Y1).sub.q of
Formula 1 is selected from substituent groups described in the
following [Table Y-1]: TABLE-US-00005 TABLE Y-1 --(L1)p--(Y1)q
##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164##
##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169##
##STR00170##
18. The compound of claim 1, wherein the compound represented by
Formula 1 is represented by any one of the following Formulas:
##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175##
##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180##
##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185##
##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190##
##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195##
##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200##
##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205##
##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210##
##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215##
##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220##
##STR00221## ##STR00222## ##STR00223## ##STR00224##
##STR00225##
19. An organic electronic device comprising: a first electrode; a
second electrode; and one or more organic material layers that are
disposed between the first electrode and the second electrode,
wherein one or more layers of the organic material layers includes
the compound of claim 1.
20. The organic electronic device of claim 19, wherein the organic
material layer includes at least one layer of a hole injection
layer, a hole transport layer, a light emitting layer, and an
electronic transport layer, and at least one layer of the hole
injection layer, the hole transport layer, the light emitting
layer, and the electronic transport layer includes the compound of
Formula 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application of
U.S. Ser. No. 13/060,248, filed on Feb. 22, 2011, which is a
national stage application of PCT/KR2009/004689, filed on on Aug.
21, 2009, which claims priority to and the benefit of Korean Patent
Application No. 10-2008-0082477, filed on Aug. 22, 2008, the entire
contents of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present specification relates to a novel compound that
is capable of largely improving an expected life span, efficiency,
electrochemical stability, and thermal stability of an organic
electronic device, and an organic electronic device using the
same.
BACKGROUND ART
[0003] An organic light emission phenomenon is an example of a
conversion of current into visible rays through an internal process
of a specific organic molecule. The organic light emission
phenomenon is based on the following mechanism. When organic
material layers are interposed between an anode and a cathode, if
voltage is applied between the two electrodes, electrons and holes
are injected from the cathode and the anode, respectively, into the
organic material layer. The electrons and the holes which are
injected into the organic material layer are recombined to form an
exciton, and the exciton is reduced to a bottom state to emit
light. An organic light emitting device which is based on the above
mechanism typically may include a cathode, an anode, and organic
material layers interposed therebetween, for example, organic
material layers including a hole injection layer, a hole transport
layer, a light emitting layer, and an electron transport layer.
[0004] The material(s) used in the organic light emitting device
are mostly pure organic materials or complexes of organic material
and metal. The material(s) used in the organic light emitting
device may be classified into a hole injection material, a hole
transport material, a light emitting material, an electron
transport material, an electron injection material, or the like,
according to its use. In connection with this, an organic material
having a p-type property, which is easily oxidized and is
electrochemically stable when it is oxidized, is mostly used as the
hole injection material or the hole transport material. Meanwhile,
an organic material having an n-type property, which is easily
reduced and is electrochemically stable when it is reduced, is
mostly used as the electron injection material or the electron
transport material. As the light emitting layer material, a
material having both p-type and n-type properties is preferable,
which is stable when it is oxidized and when it is reduced. Also, a
material having high light emission efficiency for conversion of
the exciton into light when the exciton is formed is
preferable.
[0005] Furthermore, it is preferable that the material used in the
organic light emitting device additionally have the following
properties.
[0006] First, it is preferable that the material used in the
organic light emitting device have excellent thermal stability. The
reason is that joule heat is generated by movement of electric
charges in the organic light emitting device. Recently,
4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), which has
mostly been used as the hole transport layer material, has a glass
transition temperature value of 100.degree. C. or less, thus it is
difficult to apply to an organic light emitting device requiring a
high current.
[0007] Second, in order to produce an organic light emitting device
that is capable of being driven at low voltage and has high
efficiency, holes and electrons which are injected into the organic
light emitting device must be smoothly transported to a light
emitting layer, and must not be released out of the light emitting
layer. To achieve this, a material used in the organic light
emitting device must have a proper band gap and an appropriate
highest occupied molecular orbital (HOMO) or lowest unoccupied
molecular orbital (LUMO) energy level. A LUMO energy level of
poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS),
which is currently used as a hole transport material of an organic
light emitting device manufactured using a solution coating method,
is lower than that of an organic material used as a light emitting
layer material, thus it is difficult to manufacture an organic
light emitting device having characteristics of high efficiency and
a long expected life span.
[0008] Moreover, the material used in the organic light emitting
device must have excellent chemical stability, electric charge
mobility, and interfacial characteristic with an electrode or an
adjacent layer. That is, the material used in the organic light
emitting device must be little deformed by moisture or oxygen.
Furthermore, proper hole or electron mobility must be assured so as
to balance densities of the holes and of the electrons in the light
emitting layer of the organic light emitting device to maximize the
formation of excitons. Additionally, it is preferable to have an
excellent interface characteristic with an electrode including
metal or metal oxides or an adjacent layer so as to assure
stability of the device.
[0009] Accordingly, there is a need to develop an organic material
having the above-mentioned requirements in the art.
SUMMARY OF THE INVENTION
[0010] Therefore, the inventors of the present specification aim to
provide a novel compound that is capable of satisfying conditions
required of a material which may be used for an organic light
emitting device and an organic electronic device, for example, a
proper energy level, electrochemical stability, and thermal
stability, and is capable of largely improving an expected life
span and efficiency of the organic electronic device, and an
organic electronic device using the same.
[0011] The present specification provides a compound that is
represented by the following Formula 1:
##STR00001##
[0012] wherein in Formula 1, R3 and R4 are bonded to each other to
form an aromatic ring,
[0013] at least one of a group at which an aromatic ring is not
formed among R1 to R4, a substituent group that is substituted at
an aromatic ring that is formed by bonding R3 and R4 to each other,
and R5 to R8 is -(L1)p-(Y1)q, herein, p is an integer of 0 to 10, q
is an integer of 1 to 10, the remains are each independently
-(L2)r-(Y2)s, herein, r is an integer of 0 to 10, and s is an
integer of 1 to 10,
[0014] X is -(A)m--(B)n, herein, m is an integer of 0 to 10, and n
is independently an integer of 1 to 10,
[0015] A is an arylene group having 6 to 12 carbon atoms; an
alkenylene group; a fluorenylene group; or a heteroarylene group
including one or more of N, O, and S atoms,
[0016] in the case where m is 0, B is hydrogen; deuterium; an alkyl
group; an alkenyl group; a silyl group; a boron group; an aryl
group having 6 to 12 carbon atoms; a fluorenyl group; or a hetero
ring group including one or more of N, O, and S atoms, in the case
where m is not 0, B is hydrogen; deuterium; a halogen group; a
nitrile group; a nitro group; a hydroxy group; an alkyl group; a
cycloalkyl group; an alkoxy group; an alkylthioxy group; an
alkylsulfoxy group; an alkenyl group; a silyl group; a boron group;
an aryl group having 6 to 12 carbon atoms; a fluorenyl group; or a
hetero ring group including one or more of N, O, and S atoms and
unsubstituted or substituted by an aryl group having 6 to 12 carbon
atoms,
[0017] L1 and L2 are the same as or different from each other, and
are each independently an arylene group having 6 to 12 carbon
atoms; an alkenylene group; a fluorenylene group; a carbazolylene
group; or a heteroarylene group including one or more of N, O, and
S atoms,
[0018] Y1 is a carbazole group unsubstituted or substituted by at
least one of a phenyl group, a biphenyl group, a terphenyl group, a
naphthyl group, an anthracenyl group, a phenanthryl group, a
perylenyl group, a chrysenyl group, a hetero ring group, and an
alkylamine group; or a benzocarbazole group unsubstituted or
substituted by at least one of a phenyl group, a biphenyl group, a
terphenyl group, a naphthyl group, an anthracenyl group, a
phenanthryl group, a perylenyl group, a chrysenyl group, a hetero
ring group, and an alkylamine group,
[0019] Y2 is hydrogen; deuterium; a halogen group; a nitrile group;
a nitro group; a hydroxy group; an alkyl group; a cycloalkyl group;
an alkoxy group; an alkylthioxy group; an alkylsulfoxy group; an
alkenyl group; a silyl group; a boron group; an alkylamine group; a
fluorenyl group; a carbazole group; or a hetero ring group
including one or more of N, O, and S atoms, and
[0020] in the case where two or more of A, B, L1, L2, Y1, or Y2 are
provided, they are the same as or different from each other.
[0021] Furthermore, the present specification provides an organic
electronic device including a first electrode; a second electrode;
and one or more organic material layers that are disposed between
the first electrode and the second electrode, in which one or more
layers of the organic material layers include the compound of
Formula 1.
[0022] A compound of the present specification may be used as an
organic material layer material, for example, a hole injection
material, a hole transport material, a light emitting material, an
electron transport material, an electron injection material, and
the like, and particularly, the hole injection material and/or the
hole transport material in an organic electronic device. In the
case where the compound of the present specification is used in an
organic light emitting device and an organic electronic device, a
driving voltage of the device can be reduced, light efficiency can
be improved, and an expected life span characteristic of the device
can be improved due to thermal stability of the compound.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 illustrates an example of an organic light emitting
device that includes a substrate 1, an anode 2, a light emitting
layer 3, and a cathode 4.
[0024] FIG. 2 illustrates an example of an organic light emitting
device that includes a substrate 1, an anode 2, a hole injection
layer 5, a hole transport layer 6, a light emitting layer 7, an
electron transport layer 8, and a cathode 4.
[0025] FIG. 3 is an MS data of intermediate 1-E-1 in Examples of
the present specification.
[0026] FIG. 4 is a MS data of intermediate 1-E-2 in the Examples of
the present specification.
[0027] FIG. 5 is an MS data of intermediate 5-A-1 in the Examples
of the present specification.
[0028] FIG. 6 is an MS data of compound 28 in the Examples of the
present specification.
[0029] FIG. 7 is an MS data of intermediate 2-B-1 in the Examples
of the present specification.
[0030] FIG. 8 is an MS data of compound 37 in the Examples of the
present specification.
[0031] FIG. 9 is an MS data of compound 42 in the Examples of the
present specification.
DETAILED DESCRIPTION
[0032] Hereinafter, the present specification will be described in
detail.
[0033] A compound according to the present specification is
represented by Formula 1.
##STR00002##
[0034] In Formula 1, R3 and R4 are bonded to each other to form an
aromatic ring, at least one of a group at which an aromatic ring is
not formed among R1 to R4, a substituent group that is substituted
at an aromatic ring that is formed by bonding R3 and R4 to each
other, and R5 to R8 is -(L1)p-(Y1)q, herein, p is an integer of 0
to 10, q is an integer of 1 to 10, the remains are each
independently -(L2)r-(Y2)s, herein, r may be an integer of 0 to 10,
and s may be an integer of 1 to 10.
[0035] In Formula 1, X is -(A)m-(B)n, herein, m may be an integer
of 0 to 10, and n may be independently an integer of 1 to 10.
[0036] In Formula 1, A may be an arylene group having 6 to 12
carbon atoms; an alkenylene group; a fluorenylene group; or a
heteroarylene group including one or more of N, O, and S atoms.
[0037] In Formula 1, in the case where m is 0, B may be hydrogen;
deuterium; an alkyl group; an alkenyl group; a silyl group; a boron
group; an aryl group having 6 to 12 carbon atoms; a fluorenyl
group; or a hetero ring group including one or more of N, O, and S
atoms, and in the case where m is not 0, B may be hydrogen;
deuterium; a halogen group; a nitrile group; a nitro group; a
hydroxy group; an alkyl group; a cycloalkyl group; an alkoxy group;
an alkylthioxy group; an alkylsulfoxy group; an alkenyl group; a
silyl group; a boron group; an aryl group having 6 to 12 carbon
atoms; a fluorenyl group; or a hetero ring group including one or
more of N, O, and S atoms and unsubstituted or substituted by an
aryl group having 6 to 12 carbon atoms.
[0038] In Formula 1, L1 and L2 may be the same as or different from
each other, and may be each independently an arylene group having 6
to 12 carbon atoms; an alkenylene group; a fluorenylene group; a
carbazolylene group; or a heteroarylene group including one or more
of N, O, and S atoms.
[0039] In Formula 1, Y1 may be a carbazole group unsubstituted or
substituted by at least one of a phenyl group, a biphenyl group, a
terphenyl group, a naphthyl group, an anthracenyl group, a
phenanthryl group, a perylenyl group, a chrysenyl group, a hetero
ring group, and an alkylamine group; or a benzocarbazole group
unsubstituted or substituted by at least one of a phenyl group, a
biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl
group, a phenanthryl group, a perylenyl group, a chrysenyl group, a
hetero ring group, and an alkylamine group.
[0040] In Formula 1, Y2 may be hydrogen; deuterium; a halogen
group; a nitrile group; a nitro group; a hydroxy group; an alkyl
group; a cycloalkyl group; an alkoxy group; an alkylthioxy group;
an alkylsulfoxy group; an alkenyl group; a silyl group; a boron
group; an alkylamine group; a fluorenyl group; a carbazole group;
or a hetero ring group including one or more of N, O, and S
atoms.
[0041] In Formula 1, in the case where two or more of A, B, L1, L2,
Y1, or Y2 are provided, they are the same as or different from each
other.
[0042] In Formula 1, Y1 may be any one of the following Formulas 2
to 5.
##STR00003##
[0043] In Formulas 2 to 5, A1 to A8 are each independently a phenyl
group, a biphenyl group, a terphenyl group, a naphthyl group, an
anthracenyl group, a phenanthryl group, a perylenyl group, a
chrysenyl group, a hetero ring group, or an alkylamine group, a1 is
an integer of 0 to 8, a2 is an integer of 0 to 4, a3 is an integer
of 0 to 6, a4 is an integer of 0 to 7, a6 is an integer of 0 to 4,
a8 is an integer of 0 to 6, 0.ltoreq.a6+a8.ltoreq.9, and in the
case where two or more of A1, A2, A3, A4, A6, and A8 are provided,
they are the same as or different from each other.
[0044] In Formulas 2 to 5, A5 and A7 may be each independently a
phenyl group, a biphenyl group, a terphenyl group, a naphthyl
group, an anthracenyl group, a phenanthryl group, a perylenyl
group, or a chrysenyl group.
[0045] In Formulas 2 to 5, a1 to a4, a6, and a8 may be each
independently an integer of 0 to 4.
[0046] In Formulas 2 to 5, a1 to a4, a6, and a8 may be each
independently 0 or 1.
[0047] In Formulas 2 to 5, a1 to a4, a6, and a8 may be 0.
[0048] The compound represented by Formula 1 may be represented by
the following Formula 6.
##STR00004##
[0049] In Formula 6, at least one of R1 to R10 is -(L1)p-(Y1)q, the
remains are each independently -(L2)r-(Y2)s, and herein, X, L1, L2,
Y1, Y2, p, q, r, and s are the same as those defined by Formula
1.
[0050] In an exemplary embodiment of the present specification, at
least one of L1 and L2 of Formula 1 or 6 may be a direct bond.
Specifically, in the case where L1 of Formula 1 or 6 is the direct
bond, p is 0, and in the case where L2 of Formula 1 or 6 is the
direct bond, r is 0.
[0051] In the exemplary embodiment of the present specification, L1
and L2 of Formula 1 or 6 may be the direct bond. Specifically, in
the case where L1 and L2 of Formula 1 or 6 are the direct bond, p
and r are 0.
[0052] In the exemplary embodiment of the present specification, Y2
of Formula 1 or 6 may be hydrogen.
[0053] In the exemplary embodiment of the present specification, L1
and L2 of Formula 1 or 6 may be the direct bond, and Y2 of Formula
1 or 6 may be hydrogen.
[0054] The compound represented by Formula 1 may be represented by
any one of the following Formulas 7 to 14.
##STR00005## ##STR00006## ##STR00007##
[0055] In Formulas 7 to 14, R1, R2, and E1 to E9 are each
independently -(L1)p-(Y1)q or -(L2)r-(Y2)s, and herein, X, L1, L2,
Y1, Y2, p, q, r, and s are the same as those defined by Formula
1.
[0056] In Formulas 7 to 14, A1 to A8 are each independently a
phenyl group, a biphenyl group, a terphenyl group, a naphthyl
group, an anthracenyl group, a phenanthryl group, a perylenyl
group, a chrysenyl group, a hetero ring group, or an alkylamine
group, a1 is an integer of 0 to 8, a2 is an integer of 0 to 4, a3
is an integer of 0 to 6, a4 is an integer of 0 to 7, a6 is an
integer of 0 to 4, a8 is an integer of 0 to 6,
0.ltoreq.a6+a8.ltoreq.9, e9 is an integer of 0 to 5, and in the
case where two or more of A1, A2, A3, A4, A6, A8, and E9 are
provided, they may be the same as or different from each other.
[0057] In Formulas 7 to 14, at least one of L1 and L2 may be a
direct bond. Specifically, in the case where L1 of Formulas 7 to 14
is the direct bond, p is 0, and in the case where L2 of Formulas 7
to 14 is the direct bond, r is 0.
[0058] In Formulas 7 to 14, L1 and L2 may be the direct bond.
Specifically, in the case where L1 and L2 of Formulas 7 to 14 are
the direct bond, p and r are 0.
[0059] In the exemplary embodiment of the present specification, Y2
of Formulas 7 to 14 may be hydrogen.
[0060] In the exemplary embodiment of the present specification, L1
and L2 of Formulas 7 to 14 may be the direct bond, and Y2 of
Formulas 7 to 14 may be hydrogen. Specifically, at least one of R1,
R2, and E1 to E9 of Formulas 7 to 14 may be hydrogen.
[0061] In the exemplary embodiment of the present specification, A5
and A7 of Formulas 9, 10, 13, and 14 may be each independently a
phenyl group, a biphenyl group, a terphenyl group, a naphthyl
group, an anthracenyl group, a phenanthryl group, a perylenyl
group, or a chrysenyl group.
[0062] In Formulas 7 to 14, a1 to a4, a6, a8, and e9 may be each
independently an integer of 0 to 4.
[0063] In Formulas 7 to 14, a1 to a4, a6, a8, and e9 may be each
independently 0 or 1.
[0064] In Formulas 7 to 14, a1 to a4, a6, a8, and e9 may be 0.
[0065] The compound represented by Formula 1 may be represented by
any one of the following Formulas 15 to 30.
##STR00008## ##STR00009## ##STR00010## ##STR00011##
[0066] In Formulas 15 to 30, R1 to R10 are each independently
-(L1)p-(Y1)q or -(L2)r-(Y2)s, and herein, X, L1, L2, Y1, Y2, p, q,
r, and s are the same as those defined by Formula 1.
[0067] In Formulas 15 to 30, A1 to A8 are each independently a
phenyl group, a biphenyl group, a terphenyl group, a naphthyl
group, an anthracenyl group, a phenanthryl group, a perylenyl
group, a chrysenyl group, a hetero ring group, or an alkylamine
group, a1 is an integer of 0 to 8, a2 is an integer of 0 to 4, a3
is an integer of 0 to 6, a4 is an integer of 0 to 7, a6 is an
integer of 0 to 4, a8 is an integer of 0 to 6,
0.ltoreq.a6+a8.ltoreq.9, and in the case where two or more of A1,
A2, A3, A4, A6, and A8 are provided, they may be the same as or
different from each other.
[0068] In Formulas 15 to 30, at least one of L1 and L2 may be a
direct bond. Specifically, in the case where L1 of Formulas 15 to
30 is the direct bond, p is 0, and in the case where L2 of Formulas
15 to 30 is the direct bond, r is 0.
[0069] In Formulas 15 to 30, L1 and L2 may be the direct bond.
Specifically, in the case where L1 and L2 of Formulas 15 to 30 are
the direct bond, p and r are 0.
[0070] In the exemplary embodiment of the present specification, Y2
of Formulas 15 to 30 may be hydrogen.
[0071] In the exemplary embodiment of the present specification, L1
and L2 of Formulas 15 to 30 may be the direct bond, and Y2 of
Formulas 15 to 30 may be hydrogen. Specifically, at least one of R1
to R10 of Formulas 15 to 30 may be hydrogen.
[0072] In the exemplary embodiment of the present specification, A5
and A7 of Formulas 23 to 30 may be each independently a phenyl
group, a biphenyl group, a terphenyl group, a naphthyl group, an
anthracenyl group, a phenanthryl group, a perylenyl group, or a
chrysenyl group.
[0073] In Formulas 23 to 30, a1 to a4, a6, and a8 may be each
independently an integer of 0 to 4.
[0074] In Formulas 23 to 30, a1 to a4, a6, and a8 may be each
independently 0 or 1.
[0075] In Formulas 23 to 30, a1 to a4, a6, and a8 may be 0.
[0076] The compound represented by Formula 1 may be represented by
any one of the following Formulas 31 to 42.
##STR00012## ##STR00013## ##STR00014## ##STR00015##
[0077] In Formulas 31 to 42, R1 to R10 are each independently
-(L1)p-(Y1)q or -(L2)r-(Y2)s, and herein, X, L1, L2, Y1, Y2, p, q,
r, and s are the same as those defined by Formula 1.
[0078] In Formulas 31 to 42, A2, A3 and A6 to A8 are each
independently a phenyl group, a biphenyl group, a terphenyl group,
a naphthyl group, an anthracenyl group, a phenanthryl group, a
perylenyl group, a chrysenyl group, a hetero ring group, or an
alkylamine group, a2 is an integer of 0 to 4, a3 is an integer of 0
to 6, a6 is an integer of 0 to 4, a8 is an integer of 0 to 6,
0.ltoreq.a6+a8.ltoreq.9, and in the case where two or more of A2,
A3, A6 and A8 are provided, they may be the same as or different
from each other.
[0079] In Formulas 31 to 42, at least one of L1 and L2 may be a
direct bond. Specifically, in the case where L1 of Formulas 31 to
42 is the direct bond, p is 0, and in the case where L2 of Formulas
31 to 42 is the direct bond, r is 0.
[0080] In Formulas 31 to 42, L1 and L2 may be the direct bond.
Specifically, in the case where L1 and L2 of Formulas 31 to 42 are
the direct bond, p and r are 0.
[0081] In the exemplary embodiment of the present specification, Y2
of Formulas 31 to 42 may be hydrogen.
[0082] In the exemplary embodiment of the present specification, L1
and L2 of Formulas 31 to 42 may be the direct bond, and Y2 of
Formulas 31 to 42 may be hydrogen. Specifically, at least one of R1
to R10 of Formulas 31 to 42 may be hydrogen.
[0083] In the exemplary embodiment of the present specification, A7
of Formulas 35 to 42 may be each independently a phenyl group, a
biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl
group, a phenanthryl group, a perylenyl group, or a chrysenyl
group.
[0084] In Formulas 31 to 42, a2, a3, a6 and a8 may be each
independently an integer of 0 to 4.
[0085] In Formulas 31 to 42, a2, a3, a6 and a8 may be each
independently 0 or 1.
[0086] In Formulas 31 to 42, a2, a3, a6 and a8 may be 0.
[0087] In Formulas 1, 6, and 7 to 42, A may be an arylene group
having 6 to 12 carbon atoms; or a heteroarylene group including one
or more of N, O, and S atoms.
[0088] In Formulas 1, 6, and 7 to 42, the heteroarylene group of A
may be a heteroarylene group including one or more N atoms.
Specifically, the heteroarylene group of A may be a divalent
quinazoline group, a divalent carbazole group, or a divalent
pyridine group.
[0089] In Formulas 1, 6, and 7 to 42, in the case where m is 0, B
may be an aryl group having 6 to 12 carbon atoms; a fluorenyl
group; or a hetero ring group including one or more of N, O, and S
atoms.
[0090] In Formulas 1, 6, and 7 to 42, in the case where m is not 0,
B may be hydrogen; a nitrile group; a silyl group; an aryl group
having 6 to 12 carbon atoms; a fluorenyl group; or a hetero ring
group including one or more of N, O, and S atoms and unsubstituted
or substituted by an aryl group having 6 to 12 carbon atoms.
[0091] In Formulas 1, 6, and 7 to 42, A is an arylene group having
6 to 12 carbon atoms; or a heteroarylene group including one or
more N atoms, in the case where m is 0, B may be an aryl group
having 6 to 12 carbon atoms; a fluorenyl group; or a hetero ring
group including one or more of N, O, and S atoms, and in the case
where m is not 0, B may be hydrogen; a nitrile group; a silyl
group; an aryl group having 6 to 12 carbon atoms; a fluorenyl
group; or a hetero ring group including one or more of N, O, and S
atoms and unsubstituted or substituted by an aryl group having 6 to
12 carbon atoms.
[0092] In Formulas 1, 6, and 7 to 42, m may be an integer of 0 to
2.
[0093] In Formulas 1, 6, and 7 to 42, n may be 1.
[0094] In Formulas 1, 6, and 7 to 42, m may be an integer of 0 to
2, and n may be 1.
[0095] In Formulas 1, 6, and 7 to 42, A is an arylene group having
6 to 12 carbon atoms; or a heteroarylene group including one or
more N atoms, m is an integer of 0 to 2, n is 1, in the case where
m is 0, B may be an aryl group having 6 to 12 carbon atoms; a
fluorenyl group; or a hetero ring group including one or more of N,
O, and S atoms, and in the case where m is not 0, B may be
hydrogen; a nitrile group; a silyl group; an aryl group having 6 to
12 carbon atoms; a fluorenyl group; or a hetero ring group
including one or more of N, O, and S atoms and unsubstituted or
substituted by an aryl group having 6 to 12 carbon atoms.
[0096] X of Formula 1 may be selected from substituent groups
described in the following [Table A-1], but is not limited
thereto.
TABLE-US-00001 TABLE A-1 ##STR00016## ##STR00017## ##STR00018##
##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023##
##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028##
##STR00029## ##STR00030## ##STR00031## ##STR00032##
##STR00033##
[0097] -(L1)p-(Y1)q of Formula 1 may be selected from substituent
groups described in the following [Table Y-1], but is not limited
thereto.
TABLE-US-00002 TABLE Y-1 --(L1)p--(Y1)q ##STR00034## ##STR00035##
##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041## ##STR00042## ##STR00043## ##STR00044##
[0098] In the present specification, an alkyl group, an alkoxy
group, an alkenyl group, an alkylthioxy group, an alkylsulfoxy
group, and an alkylamine group may be a straight chain or a
branched chain. The number of carbon atoms of the alkyl group, the
alkoxy group, the alkenyl group, the alkylthioxy group, the
alkylsulfoxy group, and the alkylamine group is not particularly
limited, but it is preferable that the number be in the range of 1
to 30, which is the range that does not provide sterical
hindrance.
[0099] In the present specification, the cycloalkyl group is not
particularly limited, but the number of carbon atoms thereof is
preferably 3 to 60, and particularly, it is preferable that the
cycloalkyl group be a cyclopentyl group or a cyclohexyl group.
[0100] In the present specification, as the alkenyl group, the
alkenyl group having 2 to 40 carbon atoms is preferable, and in
detail, the alkenyl group that is substituted with the aryl group
such as the stylbenzyl group and the styrenyl group is preferable,
but the alkenyl group is not limited thereto.
[0101] In the present specification, the aryl group may be a
monocycle or a polycycle. As examples of the monocyclic aryl group,
there are the phenyl group, the biphenyl group, the terphenyl
group, stilbene, and the like, and as examples of the polycyclic
aryl group, there are the naphthyl group, the anthracenyl group,
the phenanthryl group, the perylenyl group, the chrysenyl group,
the fluoranthenyl group, and the like, but the scope of the present
specification is not limited thereto.
[0102] In the present specification, the hetero ring group is a
ring group having a heteroatom of O, N or S, and the number of
carbon atoms thereof is not particularly limited, but it is
preferable that the number of carbon atoms be 3 to 60. As examples
of the hetero ring group, there are a thiophene group, a furane
group, a pyrol group, an imidazole group, a triazol group, an
oxazol group, an oxadiazol group, a triazol group, a pyridyl group,
a pyridazine group, a quinolynyl group, an isoquinoline group, an
acrydyl group and the like, and the compounds that have the
following Structural Formulas are preferable, but the examples are
not limited thereto.
##STR00045##
[0103] In the present specification, as examples of the halogen
group, there are fluorine, chlorine, bromine, or iodine.
[0104] In the present specification, it is preferable that the
fluorenyl group be the compound of the following Structural
Formula, but the fluorenyl group is not limited thereto.
##STR00046##
[0105] In the exemplary embodiment of the present specification,
the compound represented by Formula 1 may be represented by any one
of the following Formulas, but is not limited thereto.
##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051##
##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056##
##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061##
##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##
##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071##
##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076##
##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081##
##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086##
##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091##
##STR00092## ##STR00093## ##STR00094## ##STR00095##
##STR00096##
[0106] The conjugation length of the compound has a close
relationship with an energy band gap. In detail, the energy band
gap is reduced as the conjugation length of the compound increases.
As described above, since a conjugation is limited in the core of
the compound of Formula 1, the core has a large energy band
gap.
[0107] As described above, in the present specification, various
substituent groups may be introduced to L1, L2, X, Y1, or Y2
positions of the core structure having the large energy band gap so
as to synthesize compounds having various energy band gaps.
Generally, it is easy to control the energy band gap by introducing
the substituent groups into the core structure having the large
energy band gap, but it is difficult to significantly control the
energy band gap by introducing the substituent groups into the core
structure having the small energy band gap. Furthermore, in the
present specification, it is possible to control HOMO (highest
occupied molecular orbital) and LUMO (lowest unoccupied molecular
orbital) energy levels of the compound by introducing various
substituent groups into the L1, L2, X, Y1, or Y2 positions of the
aforementioned core structure.
[0108] Additionally, by introducing various substituent groups into
the aforementioned core structure, compounds having intrinsic
characteristics of the introduced substituent groups may be
synthesized. For example, the substituent groups, which are applied
to a hole injection layer material, a hole transport layer
material, a light emitting layer material, and an electron
transport layer material used during the production of the organic
light emitting device and the organic electronic device, may be
introduced into the core structure so as to synthesize materials
capable of satisfying the requirements of each organic material
layer.
[0109] Furthermore, various substituent groups may be introduced
into the core structure so as to precisely control the energy band
gap, and to improve interfacial characteristics with organic
material layers, and make the purpose of the material various.
[0110] In addition, if an appropriate substituent is introduced to
the structure of Formula 1, energy band gap and stability may be
ensured at a triplet state. From these results, various
phosphorescence dopants having a red color to a blue color may be
used and applied to light emitting layers of fluorescent and
phosphorescent devices.
[0111] In the present specification, in the case where the compound
of Formula 1 is applied together with the dopant to the light
emitting layer, the dopant may be used by selecting any one of the
following Dp-1 to Dp-15, but is not limited thereto.
##STR00097## ##STR00098## ##STR00099##
[0112] In addition, since the compound of Formula 1 has a high
glass transition temperature (Tg), the compound has excellent
thermal stability. Such increase in thermal stability is an
important factor providing driving stability to the device.
[0113] Furthermore, the compound of Formula 1 may be used to form
the organic material layer using a vacuum deposition process or a
solution coating process during the production of the organic
electronic device. In connection with this, examples of the
solution coating process include spin coating, dip coating, inkjet
printing, screen printing, a spray process, roll coating, and the
like, but are not limited thereto.
[0114] The organic electronic device of the present specification
may be produced using known materials through a known process,
modified only in that one or more layers of organic material layers
include the compound of the present specification, that is, the
compound of Formula 1. The compound according to the present
specification may be used as a hole injection material, a hole
transport material, a light emitting material, an electron
transport material, an electron injection material, and the like,
and it is more preferable that the compound be used as the light
emitting material in the organic electronic device according to the
present specification.
[0115] In addition, on the basis of the application of the compound
according to the present specification to the organic light
emitting device, those who are skilled in the art can use the
compound according to the present specification in other organic
electronic devices. The organic electronic device according to the
present specification includes an organic light emitting device, an
organic phosphorescent device, an organic solar cell, an organic
photoconductor (OPC), and an organic transistor.
[0116] The organic material layer of the organic electronic device
of the present specification may have a single layer structure, or
alternatively, a multilayered structure in which at least two
organic material layers are layered. For example, the organic light
emitting device of the present specification may have a structure
including a hole injection layer, a hole transport layer, a light
emitting layer, an electron transport layer, an electron injection
layer, and the like as the organic material layer. However, the
structure of the organic light emitting device is not limited
thereto, but may include a smaller number of organic material
layers. The structure of the organic light emitting device of the
present specification is illustrated in FIGS. 1 and 2, but is not
limited thereto.
[0117] The organic light emitting device of the present
specification may be produced, for example, by sequentially
layering a first electrode, an organic material layer, and a second
electrode on a substrate. In connection with this, a physical vapor
deposition (PVD) method, such as a sputtering method or an e-beam
evaporation method, may be used, but the method is not limited
thereto.
[0118] The method for manufacturing the compound of Formula 1 and
the manufacturing of an organic light emitting device using the
same will be described in detail in the following Preparation
Examples and Examples. However, the following Preparation Examples
and Examples are set forth to illustrate the present specification,
but the scope of the present specification is not limited
thereto.
[0119] The compound of Formula 1 according to the present
specification may be manufactured with multistage chemical
reactions. The manufacturing of the compounds will be described in
the following Synthesis Examples and Preparation Examples. As
described in the following Synthesis Examples, some intermediate
compounds are first manufactured, and as described in the
Preparation Examples, the compounds of Formula 1 are manufactured
from the intermediate compounds.
Synthesis Example of Intermediate 1-A-2
##STR00100##
[0120] 1) Synthesis of Intermediate 1-A-1
[0121] .beta.-tetralone (CAS#530-93-8, 18 g, 123 mmol), and
4-bromophenylhydrazine hydrochloride (CAS#622-88-8, 29 g, 129 mmol)
were put into 300 ml of ethanol (EtOH), and the hydrochloric acid
was put thereinto in a small amount, and heated and refluxed for 1
hour under nitrogen atmosphere. After the reaction was finished,
cooling to room temperature was performed, the product was filtered
to be dried in the vacuum oven for one day and thus obtain 25 g of
intermediate 1-A-1 (10-bromo-6,7-dihydro-5H-benzo[c]carbazole)
(yield 68.8%). [M+H]=298
2) Synthesis of Intermediate 1-A-2
[0122] 25 g of the intermediate 1-A-1 was put into 400 ml of
CH.sub.3CN, and tetrachloro-1,4-benzoquinone (DDQ, chloranil,
CAS#118-75-2, 21 g, 84.7 mmol) in the solid state slowly dripped
thereinto in the cold bath condition of 0.degree. C. in an amount
of the same equivalent as intermediate 1-A-1. After the reaction
was finished, NaOH (10%) and water were put into the reaction
solution, and the organic layer was extracted. The reaction
solution was concentrated and recrystallized with hexane to
manufacture 21 g of intermediate 1-A-2
(10-bromo-7H-benzo[c]carbazole) (yield 84.7%). [M+H]=296
Synthesis Example of Intermediate 1-B-3
##STR00101##
[0123] 1) Synthesis of Intermediate 1-B-1
[0124] After the 1-naphthylboronic acid (CAS#13922-41-3, 17 g, 100
mmol) and 2-chloro-2-nitrobenzene (CAS#88-73-3, 16 g, 100 mmol)
were dissolved in 200 ml of toluene and 100 ml of ethanol,
potassium carbonate (CAS#584-08-7, 41 g, 300 mmol) was dissolved in
water to be put into the reaction solution, and heating and
agitation were performed for 30 minutes. After 30 minutes,
tetrakis(triphenylphosphine) palladium(0) (CAS#14221-01-3, 1.7 g,
1.5 mmol) was put, and additionally reacted for 2 hours. After the
reaction was finished, an excessive amount of water was put,
extraction with ethyl acetate (EA) was carried out to obtain the
organic layer, and column purification was carried out to obtain 18
g of intermediate 1-B-1 (yield 75.5%). [M]=249
2) Synthesis of Intermediate 1-B-2
[0125] 20 g of obtained intermediate 1-B-1 (80 mmol) was put into
200 ml of dichloromethane (CH.sub.2Cl.sub.2), and bromine
(Br.sub.2, CAS#7726-95-6, 4.3 ml, 84 mmol) slowly dripped in the
ice bath at 0.degree. C. for 20 minutes. After addition was
finished, the reaction solution was agitated in the room
temperature state for about one day. After the reaction was
finished, in the reaction solution, residual bromine was removed
with water and sodium thiosulfate (Na.sub.2S.sub.2O.sub.3,
CAS#10102-17-7) in the aqueous solution state, and extraction with
dichloromethane was carried out. After extraction, the solvent was
concentrated by the rotary evaporator, and 22.8 g of compound 1-B-2
(yield 86.4%) was obtained through column purification.
[M+H]=328
3) Synthesis of Intermediate 1-B-3
[0126] 20 g of obtained intermediate 1-B-2 was put into
triethylphosphite (P(OEt).sub.3, CAS#122-52-1, 42 ml), and heating
and agitation were carried out at 180.degree. C. for 8 hours. After
the reaction was finished, residual P(OEt).sub.3 was removed
through vacuum distillation, and extraction was carried out by
using EA. Anhydrous magnesium sulfate (MgSO.sub.4, CAS#7487-88-9)
was put into extracted EA to remove water, and column purification
was carried out to obtain 11.6 g of intermediate 1-B-3
(5-bromo-7H-benzo[c]carbazole) (yield 64.3%).
Synthesis Example of Intermediate 1-C-3
##STR00102##
[0127] 1) Synthesis of Intermediate 1-C-1
[0128] By the same method as the method mentioned in US Patent
Laid-Open No. 2009-0076076, aluminum chloride (AlCl.sub.3,
CAS#7446-70-0, 31.9 g, 239 mmol) was put into 30 ml of
CH.sub.2Cl.sub.2 under nitrogen atmosphere, and agitated at
0.degree. C. for 10 minutes, and .beta.-tetralone (17.5 g, 120
mmol) was then added. Agitation was carried out for 20 minutes, and
Br.sub.2 (6.74 ml, 131 mmol) was slowly added at the same
temperature. After addition of bromine was finished, the reaction
solution was further agitated at room temperature for 1 hour. After
the reaction was finished, the reaction solution was poured into
the ice bath and extracted with EA. After the extracted organic
material was dried by MgSO.sub.4 and concentrated by the rotary
evaporator, the concentrated solution was subjected to column
purification to obtain 19 g of intermediate 1-C-1
(7-bromo-3,4-dihydronaphthalen-2(1H)-one) (yield 71.1%).
[M]=225
2) Synthesis of Intermediate 1-C-2
[0129] 23 g of intermediate 1-C-2
(2-bromo-6,7-dihydro-5H-benzo[c]carbazole) (yield 88.7%) was
obtained by the same synthesis method as intermediate 1-A-1 using
intermediate 1-C-1 (20 g, 89 mmol) and phenylhydrazine
hydrochloride (CAS#59-88-1, 12.9 g, 89 mmol). [M+H]=299
3) Synthesis of Intermediate 1-C-3
[0130] Intermediate 1-C-2 (20 g, 67 mmol) was subjected to the same
procedure as the synthesis method of intermediate 1-A-2 to obtain
13 g of intermediate 1-C-3 (2-bromo-7H-benzo[c]carbazole) (yield
64.7%).
Synthesis Example of Intermediate 1-D-2
##STR00103##
[0131] 1) Synthesis of Intermediate 1-D-1
[0132] 6-bromo-2-tetralone (CAS#4133-35-1, 30 g, 133 mmol) and
phenylhydrazine hydrochloride (19 g, 133 mmol) were subjected to
the same procedure as the synthesis method of intermediate 1-A-1 to
obtain intermediate 1-D-1
(3-bromo-6,7-dihydro-5H-benzo[c]carbazole). [M+H]=298
2) Synthesis of Intermediate 1-D-2
[0133] All intermediate 1-D-1 and DDQ (30 g, 133 mmol) were used,
and the same procedure as the synthesis method of intermediate
1-A-2 was carried out to obtain 25.5 g of intermediate 1-D-2
(3-bromo-7H-benzo[c]carbazole) (total yield of 1-D-1 and 1-D-2
64.6%).
Synthesis Example of Intermediate 1-E-1
##STR00104##
[0135] The same procedure as the synthesis method of intermediate
1-B-1 was carried out by using 2,4-dichloroqinazoline
(CAS#607-68-1, 10 g, 50 mmol) and phenylboronic acid (PBA,
CAS#98-80-6, 6.10 g, 50 mmol) to obtain 8.3 g of intermediate 1-E-1
(yield 68.7%). [M]=240
Synthesis Example of Intermediate 1-E-2
##STR00105##
[0137] The same procedure as the synthesis method of intermediate
1-B-1 was carried out by using 2,4-dichloroqinazoline
(CAS#607-68-1, 20 g, 100 mmol) and 4-biphenylboronic acid (PBA,
CAS#5122-94-1, 20 g, 100 mmol) to obtain 23.3 g of intermediate
1-E-2 (yield 73.2%). [M]=317
Synthesis Example of Intermediate 1-E-3
##STR00106##
[0139] The same procedure as the synthesis method of intermediate
1-B-1 was carried out by using 2,4-dichloroqinazoline
(CAS#607-68-1, 20 g, 100 mmol)) and 4-(2-pyridyl)-phenylboronic
acid (CAS#170230-27-0, 20 g, 100 mmol) to obtain 23.8 g of
intermediate 1-E-3 (yield 74.9%). [M]=317
Synthesis Example of Intermediate 1-E-4
##STR00107##
[0141] The same procedure as the synthesis method of intermediate
1-B-1 was carried out by using 2,4-dichloroqinazoline
(CAS#607-68-1, 20 g, 100 mmol) and 9,9-dimethyl-9H-fluoren-2-yl
boronic acid (CAS#333432-28-3, 23.8 g, 100 mmol) to obtain 18.6 g
of intermediate 1-E-4 (yield 52.1%). [M]=356
Synthesis Example of Intermediate 1-E-5
##STR00108##
[0143] The same procedure as the synthesis method of intermediate
1-B-1 was carried out by using 2,4-dichloroqinazoline
(CAS#607-68-1, 20 g, 100 mmol) and 2-naphthyl boronic acid
(CAS#32316-92-0, 18.1 g, 100 mmol) to obtain 26.7 g of intermediate
1-E-5 (yield 91.3%). [M]=290
Synthesis Example of Intermediate 2-E-1
##STR00109##
[0145] 12 g of synthesized intermediate 1-E-1 (50 mmol) and
4-chlorophenyl boronic acid (CAS#1679-18-1, 8.6 g, 55 mmol) were
subjected to the same procedure as the synthesis method of
intermediate 1-B-1 to obtain 11.8 g of intermediate 2-E-1 (yield
74.4%). [M]=316
Synthesis Example of Intermediate 2-A-1
##STR00110##
[0147] 25.5 g of intermediate 2-A-1 (yield 82.4%) was obtained by
using 20 g of intermediate 1-A-2 (67.5 mmol) and
N-phenyl-9H-carbazole-3-yl boronic acid (CAS#854952-58-2, 20.4 g,
70.9 mmol) under the same condition as the synthesis method of
intermediate 1-B-1. [M+H]=458
Synthesis Example of Intermediate 2-A-2
##STR00111##
[0149] 22.2 g of intermediate 2-A-2 (yield 71.6%) was obtained by
using 20 g of intermediate 1-A-2 (67.5 mmol) and
N-phenyl-9H-carbazole-2-yl boronic acid (CAS#1001911-63-2, 20.4 g,
70.9 mmol) under the same condition as the synthesis method of
intermediate 1-B-1. [M+H]=458
Synthesis Example of Intermediate 2-B-1
##STR00112##
[0151] 13.9 g of intermediate 2-B-1 (yield 74.7%) was obtained by
using 12 g of intermediate 1-B-3 (41 mmol) and
N-phenyl-9H-carbazole-3-yl boronic acid (12.2 g, 43 mmol) under the
same condition as the synthesis method of intermediate 1-B-1.
[M+H]=458
Synthesis Example of Intermediate 2-B-2
##STR00113##
[0153] 17.4 g of intermediate 2-B-2 (yield 75.1%) was obtained by
using 15 g of intermediate 1-B-3 (50.6 mmol) and
N-phenyl-9H-carbazole-2-yl boronic acid (15.3 g, 53.2 mmol) under
the same condition as the synthesis method of intermediate 1-B-1.
[M+H]=458
Synthesis Example of Intermediate 2-C-1
##STR00114##
[0155] 10.8 g of intermediate 2-C-1 (yield 69.8%) was obtained by
using 10 g of intermediate 1-C-3 (34 mmol) and
N-phenyl-9H-carbazole-3-yl boronic acid (10.7 g, 37 mmol) under the
same condition as the synthesis method of intermediate 1-B-1.
[M+H]=458
Synthesis Example of Intermediate 2-C-2
##STR00115##
[0157] 8.7 g of intermediate 2-C-2 (yield 70.1%) was obtained by
using 8 g of intermediate 1-C-3 (27 mmol) and
N-phenyl-9H-carbazole-2-yl boronic acid (8.1 g, 28.3 mmol) under
the same condition as the synthesis method of intermediate 1-B-1.
[M+H]=458
Synthesis Example of Intermediate 2-D-1
##STR00116##
[0159] 10.7 g of intermediate 2-D-1 (yield 69.0%) was obtained by
using 10 g of intermediate 1-D-2 (34 mmol) and
N-phenyl-9H-carbazole-3-yl boronic acid (10.2 g, 37 mmol) under the
same condition as the synthesis method of intermediate 1-B-1.
[M+H]=458
Synthesis Example of Intermediate 2-D-2
##STR00117##
[0161] 11.2 g of intermediate 2-D-2 (yield 65.7%) was obtained by
using 11 g of intermediate 1-D-2 (37 mmol) and
N-phenyl-9H-carbazole-2-yl boronic acid (11.2 g, 39 mmol) under the
same condition as the synthesis method of intermediate 1-B-1.
[M+H]=458
[0162] The method of manufacturing the compounds of Formula 1
manufactured by using the intermediate compounds manufactured in
the Synthesis Examples is described below, but is not limited
thereto.
Preparation Example 1
Synthesis of Compound 1
[0163] 10 g of synthesized intermediate 2-A-1 (21.8 mmol) was put
together with copper (Cu, CAS#7440-50-8, 2.77 g, 43.6 mmol) and
potassium phosphate (K.sub.3PO.sub.4, 13.8 g, 65.4 mmol) into the
iodobenzene (CAS#591-50-4) solvent (hereinafter, Ullmann
condition), and heating and agitation were carried out for one day.
After the reaction was finished, the reaction solution was cooled
to room temperature, an excessive amount of ethanol (EtOH) was put
to precipitate the compound, extraction with CHCl.sub.3 was carried
out, water was removed, and recrystallization was carried out by
using EA to obtain 9.6 g of compound 1 (yield 82.1%). [M]=534
Preparation Example 2
Synthesis of Compound 11
[0164] 7 g of synthesized intermediate 2-B-1 (15.2 mmol) and
4-iodobiphenyl (CAS#1591-31-7, 4.7 g, 16.8 mmol) were put into
xylene, sodium t-butoxide (NaOtBu, CAS#865-48-5, 2.9 g, 30.5 mmol)
was put thereinto, and heating and agitation were carried out for
30 minutes. After agitation for 30 minutes,
bis(tri-tert-butylphosphine)palladium(0) (BTP, 0.02 g,
3.05.quadrature.mol) was put thereinto, and heating and agitation
were further carried out for one day (hereinafter, Buchwald
condition). After the reaction was finished, cooling to room
temperature was carried out, an excessive amount of ethanol (EtOH)
was put to precipitate the precipitate, the precipitate was put
into N-methyl-2-pyrollidone (NMP, CAS#872-50-4), heated and
refluxed for 2 hours, and cooled to room temperature to generate
the precipitate again. The generated precipitate was washed with
ethanol (EtOH) to obtain 6.2 g of compound II (yield 66.3%).
[M]=610
Preparation Example 3
Synthesis of Compound 21
[0165] The same procedure as synthesis of compound 11 was carried
out by using 8 g of synthesized intermediate 2-C-1 (17.4 mmol) and
2-bromonaphthalene (CAS#580-13-2, 4.0 g, 19.1 mmol) to obtain 7.2 g
of compound 21 (yield 70.1%). [M]=584
Preparation Example 4
Synthesis of Compound 26
[0166] 10 g of synthesized intermediate 2-A-1 (21.8 mmol) was
slowly put together with sodium hydride (NaH (hereinafter),
CAS#7646-69-7, 1.7 g, 26.1 mmol) into anhydrous dimethylacetamide
(DMF (hereinafter), CAS#68-12-2) under nitrogen atmosphere. After
agitation at room temperature for 1 hour, 2-chloroquinazoline
(CAS#6141-13-5, 3.8 g, 23.0 mmol) was put thereinto, and agitated
at room temperature for one day. After the reaction was finished,
the generated precipitate was filtered, washed with EtOH, and
extracted with EA to obtain 9.8 g of compound 26 (yield 76.3%).
[M]=587
Preparation Example 5
Synthesis of Compound 27
[0167] The same procedure as the synthesis method of the
aforementioned compound 26 was carried out by using 9 g of
synthesized intermediate 2-A-1 (19.6 mmol) and 5.0 g of synthesized
intermediate 1-E-1 (20.6 mmol) to obtain 10.6 g of compound 27
(yield 81.7%). [M+H]=663
Preparation Example 6
Synthesis of Compound 28
[0168] The same procedure as the synthesis method of the
aforementioned compound 26 was carried out by using 8 g of
synthesized intermediate 2-A-1 (17.4 mmol) and 5.8 g of synthesized
intermediate 1-E-2 (18.3 mmol) to obtain 10.0 g of compound 28
(yield 77.4%). [M+H]=739
Preparation Example 7
Synthesis of Compound 32
[0169] The same procedure as the method of the aforementioned
compound 26 was carried out by using 12 g of synthesized
intermediate 2-B-1 (26.1 mmol) and 6.6 g of synthesized
intermediate 1-E-1 (27.4 mmol) to obtain 13.9 g of compound 32
(yield 80.3%). [M+H]=663
Preparation Example 8
Synthesis of Compound 37
[0170] The same procedure as the method of the aforementioned
compound 26 was carried out by using 15.4 g of synthesized
intermediate 2-C-1 (33.8 mmol) and 8.1 g of synthesized
intermediate 1-E-1 (33.8 mmol) to obtain 14 g of compound 37 (yield
62.9%). [M+H]=663
Preparation Example 9
Synthesis of Compound 42
[0171] The same procedure as the method of the aforementioned
compound 26 was carried out by using 11 g of synthesized
intermediate 2-D-1 (23 mmol) and 5.9 g of synthesized intermediate
1-E-1 (24 mmol) to obtain 12 g of compound 42 (yield 78.3%).
[M+H]=663
Preparation Example 10
Synthesis of Compound 49
[0172] The same procedure as the method of the aforementioned
compound 26 was carried out by using 6.5 g of synthesized
intermediate 2-A-2 (14.1 mmol) and 4.7 g of synthesized
intermediate 1-E-3 (14.9 mmol) to obtain 7.7 g of compound 49
(yield 82.7%). [M+H]=740
Preparation Example 11
Synthesis of Compound 58
[0173] The same procedure as the method of the aforementioned
compound 26 was carried out by using 8.3 g of synthesized
intermediate 2-C-2 (18.1 mmol) and 6.8 g of synthesized
intermediate 1-E-2 (19.0 mmol) to obtain 10.8 g of compound 58
(yield 76.3%). [M+H]=780
Preparation Example 12
Synthesis of Compound 67
##STR00118##
[0174] 1) Synthesis of Intermediate 3-A-1
[0175] The same procedure as the method of the aforementioned
compound 26 was carried out by using 7 g of synthesized
intermediate 1-A-2 (15.2 mmol) and 5.9 g of synthesized
intermediate 1-E-1 (24 mmol) to obtain 7.2 g of intermediate 3-A-1
(yield 94.7%). [M]=500
2) Synthesis of Compound 67
[0176] The same procedure as the method of the aforementioned
intermediate 1-B-1 was carried out by using 7 g of synthesized
intermediate 3-A-1 (14.0 mmol) and 9-phenyl-9H-carbazol-4-yl
boronic acid (CAS#1370555-65-9, 4.2 g, 14.7 mmol) to obtain 7 g of
compound 67 (yield 70%). [M+H]=663
Preparation Example 13
Synthesis of Compound 71
##STR00119##
[0177] 1) Synthesis of Intermediate 4-A-1
[0178] The same procedure as the method of the aforementioned
compound 26 was carried out by using 10 g of synthesized
intermediate 1-A-2 (33.8 mmol) and 2-chloroquinazoline
(CAS#6141-13-5, 5.8 g, 35.4 mmol) to obtain 13.3 g of intermediate
4-A-1 (yield 92.3%). [M]=424
2) Synthesis of Compound 71
[0179] The same procedure as the method of the aforementioned
intermediate 1-B-1 was carried out by using 10 g of synthesized
intermediate 4-A-1 (23.6 mmol) and
4-biphenyl-9H-carbazolyl-3-boronic acid (CAS#1028648-22-7, 9.0 g,
24.7 mmol) to obtain 17 g of compound 71 (yield 79.3%).
[M+H]=663
Preparation Example 14
Synthesis of Compound 97
##STR00120##
[0181] 10 g of synthesized intermediate 3-A-1 (20.0 mmol),
9H-carbazole (CAS#86-74-8, 3.5 g, 21 mmol), and 8.5 g of
K.sub.3PO.sub.4 (40 mmol) were put into 70 ml of xylene, and heated
and refluxed for 1 hour under nitrogen atmosphere. After one hour,
bis(dibenzylideneacetone)palladium(o) (Pd(dba).sub.2 (hereinafter),
CAS#32005-36-0, 0.34 g, 0.6 mmol) and
4,5-bis(diphenylphosphinyl)-9,9-dimethylxathene (xanphos
(hereinafter), CAS#161265-03-8, 0.34 g, 0.6 mmol) were
simultaneously put into the reaction solution, and heated and
refluxed for one day. After the reaction was finished, cooling to
room temperature was carried out, an excessive amount of EtOH was
put to generate the precipitate and thus filter the precipitate.
The filtered precipitate was agitated with an excessive amount of
water and THF, and then recrystallized with EA to obtain 8 g of
compound 97 (yield 69.1%). [M]=586
Preparation Example 15
Synthesis of Compound 98
##STR00121##
[0183] The same procedure as the method of the aforementioned
compound 97 was carried out by using 10 g of synthesized
intermediate 3-A-1 (20 mmol) and 7H-benzo[c]carbazole
(CAS#205-25-4, 4.6 g, 21 mmol) to obtain 7.7 g of compound 98
(yield 58.4%). [M+H]=663
Preparation Example 16
Synthesis of Compound 99
##STR00122##
[0184] 1) Synthesis of Intermediate 5-A-1
[0185] The same procedure as the method of the aforementioned
compound 26 was carried out by using 10 g of synthesized
intermediate 1-A-2 (33.8 mmol) and 11 g of intermediate 1-E-2 (35.4
mmol) to obtain 18.1 g of intermediate 5-A-1 (yield 90.4%).
[M]=576
2) Synthesis of Compound 99
[0186] The same procedure as the method of the aforementioned
compound 97 was carried out by using 15 g of synthesized
intermediate 5-A-1 (26 mmol) to obtain 10.6 g of compound 99 (yield
61.3%). [M+H]=663
Preparation Example 17
Synthesis of Compound 115
##STR00123##
[0187] 1) Synthesis of Intermediate 3-B-1
[0188] The same procedure as the method of the aforementioned
compound 26 was carried out by using 7 g of synthesized
intermediate 1-B-3 (23.6 mmol) and 8.9 g of intermediate 1-E-4
(24.8 mmol) to obtain 13.9 g of intermediate 3-B-1 (yield 95.4%).
[M]=616
2) Synthesis of Compound 115
[0189] The same procedure as the method of the aforementioned
compound 97 was carried out by using 10 g of synthesized
intermediate 3-B-1 (16.2 mmol) to obtain 8.5 g of compound 115
(yield 74.2%). [M+H]=703
Preparation Example 18
Synthesis of Compound 123
##STR00124##
[0190] 1) Synthesis of Intermediate 4-C-1
[0191] The same procedure as the method of the aforementioned
compound 26 was carried out by using 7 g of synthesized
intermediate 1-C-3 (23.6 mmol) and 7.9 g of intermediate 1-E-3
(24.8 mmol) to obtain 12.8 g of intermediate 4-C-1 (yield 94.1%).
[M]=577
2) Synthesis of Compound 123
[0192] The same procedure as the method of the aforementioned
compound 97 was carried out by using 10 g of synthesized
intermediate 4-C-1 (17.3 mmol) to obtain 8.3 g of compound 123
(yield 71.9%). [M+H]=664
Preparation Example 19
Synthesis of Compound 137
[0193] The same procedure as the method of the aforementioned
compound 26 was carried out by using 17.4 g of synthesized
intermediate 2-A-1 (37.9 mmol) and 11 g of synthesized intermediate
1-E-5 (37.9 mmol) to obtain 21.0 g of compound 137 (yield 77.6%).
[M+H]=713
Preparation Example 20
Synthesis of Compound 141
[0194] The same procedure as the synthesis method of compound 11
was carried out by using 7 g of synthesized intermediate 2-A-1
(15.3 mmol) and 5.1 g of synthesized intermediate 2-E-1 (16.0 mmol)
to obtain 5.5 g of compound 141 (yield 48.7%). [M+H]=739
Example
[0195] The glass substrate (corning 7059 glass) on which a thin
film of indium tin oxide (ITO) was applied in a thickness of 1,000
.ANG. was put into distilled water having the dispersing agent
dissolved therein, and washed with ultrasonic waves. The detergent
used herein was a product commercially available from Fisher Co.,
and distilled water was one which had been twice filtered by using
a filter commercially available from Millipore Co. ITO was washed
for 30 minutes, and washing with ultrasonic waves was then repeated
twice for 10 minutes by using distilled water. After washing with
distilled water was finished, washing with ultrasonic waves was
performed by using isopropyl alcohol, acetone, and methanol
solvents in the order, and drying was performed.
[0196] Hexanitrile hexaazatriphenylene (HAT-CN) was vacuum
deposited by heat in a thicknesses of 500 .ANG. on the ITO
transparent electrode thus prepared to form the hole injecting
layer. After HT1 (400 .ANG.) transporting holes was vacuum
deposited thereon, the compound described in the following Table 1
as the host was deposited under the vacuum in a thickness of 300
.ANG. together with the dopant Dp-6 compound as the light emitting
layer. Thereafter, the E1 compounds (300 .ANG.) were sequentially
vacuum deposited by heat as electron injection and transport
layers. On the electron injection and transport layers, lithium
fluoride (LiF) in a thickness of 12 .ANG. and aluminum in a
thickness of 2,000 .ANG. were subsequently deposited to form the
cathode, thereby manufacturing the organic light emitting
device.
[0197] In the aforementioned process, the deposition speed of the
organic material was maintained at 1 .ANG./sec, the deposition
speed of LiF was maintained at 0.2 .ANG./sec, and the deposition
speed of aluminum was maintained at 3 .ANG./sec to 7 .ANG./sec.
##STR00125## ##STR00126##
[0198] Examples of evaluation of the devices with respect to each
material are described below.
TABLE-US-00003 TABLE 1 Actuating Current Power voltage efficiency
efficiency Lifespan X Y Compound (V) (cd/A) (lm/w) (T95@10 mA)
coordinate coordinate Comparative H1 4.71 23.76 16.32 73 0.666
0.332 Example H2 5.32 22.21 13.50 93 0.661 0.331 Example 26 5.00
22.95 14.20 255 0.658 0.337 27 5.17 24.20 14.71 310 0.660 0.338 28
4.95 25.41 15.00 250 0.655 0.344 32 4.94 23.00 15.00 315 0.663
0.335 37 5.15 24.22 13.74 280 0.662 0.335 42 5.20 23.88 13.20 260
0.661 0.334 52 4.92 24.21 15.11 299 0.657 0.332 97 5.69 25.25 14.11
199 0.660 0.336 99 5.28 24.06 14.67 245 0.662 0.336 98 5.52 23.55
13.41 185 0.662 0.336 115 5.18 23.64 12.89 263 0.657 0.337
* * * * *